P
US7087152B2ExpiredUtilityPatentIndex 74

Wax isomerate yield enhancement by oxygenate pretreatment of feed

Assignee: EXXONMOBIL RES & ENG COPriority: Oct 8, 2002Filed: Oct 3, 2003Granted: Aug 8, 2006
Est. expiryOct 8, 2022(expired)· nominal 20-yr term from priority
Inventors:CODY IAN AMURPHY WILLIAM JHANTZER SYLVAIN
C10G 45/02B01J 29/068B01J 2229/12C10G 45/64C10G 45/62B01J 29/74B01J 29/7461B01J 37/12C10G 65/043B01J 2229/34C10G 45/60B01J 37/10
74
PatentIndex Score
9
Cited by
117
References
68
Claims

Abstract

A waxy hydrocarbon feed is catalytically dewaxed with a catalyst that has been selectively activated. The selective activation of the catalyst involves contacting the dewaxing catalyst with a feed mixture containing waxy hydrocarbon and at least one oxygenate. The process results in improved catalyst performance resulting in improved yield of isomerate at equivalent pour.

Claims

exact text as granted — not AI-modified
The invention claimed is: 
     
       1. A process for catalytically dewaxing a waxy mineral hydrocarbon feed which comprises:
 (a) forming a mixture containing the waxy hydrocarbon feed and from 100 wppm to 10000 wppm of at least one oxygenate; and 
 (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules under conditions effective to catalytically dewax the feed. 
 
     
     
       2. The process of  claim 1  wherein the waxy hydrocarbon feed contains at least about 15 wt. % wax, based on feed. 
     
     
       3. The process of  claim 1  wherein the oxygenate is at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether. 
     
     
       4. The process of  claim 1  wherein the oxygenate is water. 
     
     
       5. The process of  claim 1  wherein the amount of oxygenate in the mixture is at least about 100 wppm, measured as oxygen. 
     
     
       6. The process of  claim 1  wherein the dewaxing catalyst contains at least one molecular sieve containing at least one 10 or 12 ring channel. 
     
     
       7. The process of  claim 6  wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 
     
     
       8. The process of  claim 6  wherein the molecular sieve is at least one of zeolite beta, ZSM-12, MCM-68, SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 
     
     
       9. The process of  claim 6  wherein the molecular sieve is ZSM-48. 
     
     
       10. The process of  claim 1  wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400° C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr −1  and a treat gas rate of from 45 to 1780 m 3 /m 3 . 
     
     
       11. The process of  claim 1  wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 
     
     
       12. The process of  claim 11  wherein the improved yield is at least 4 relative percent. 
     
     
       13. The process of  claim 1  wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 
     
     
       14. The process of  claim 1  wherein the dewaxing catalyst bears a metal hydrogenation component. 
     
     
       15. The process of  claim 14  wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 
     
     
       16. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least 15 wt. % wax, based on hydrocarbon feed, which comprises:
 (a) forming a mixture containing the hydrocarbon feed and at least one oxygenate wherein the amount of oxygenate in the mixture is at least about 100 wppm to 10000 wppm measured as oxygen, and 
 (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains at least one molecular sieve containing at least one 10 or 12 ring channel under conditions effective to catalytically dewax the feed. 
 
     
     
       17. The process of  claim 16  wherein the oxygenate is at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether. 
     
     
       18. The process of  claim 16  wherein the oxygenate is water. 
     
     
       19. The process of  claim 16  wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-7, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 
     
     
       20. The process of  claim 16  wherein the molecular sieve is at least one of zeolite beta, ZSM-12, MCM-68, SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 
     
     
       21. The process of  claim 19  wherein the molecular sieve is ZSM-48. 
     
     
       22. The process of  claim 16  wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400° C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr −1  and a treat gas rate of from 45 to 1780 m 3 /m 3 . 
     
     
       23. The process of  claim 16  wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 
     
     
       24. The process of  claim 23  wherein the improved yield is at least 4 relative percent. 
     
     
       25. The process of  claim 16  wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 
     
     
       26. The process of  claim 16  wherein the dewaxing catalyst bears a metal hydrogenation component. 
     
     
       27. The process of  claim 26  wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 
     
     
       28. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least about 15 wt. % wax, based on hydrocarbon feed, which comprises:
 (a) forming a mixture containing the hydrocarbon feed and at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether wherein the amount of oxygen in the mixture is at least about 100 wppm to 10000 wppm, measured as oxygen, and 
 (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains at least one molecular sieve containing at least one 10 or 12 ring channel under conditions effective to catalytically dewax the feed. 
 
     
     
       29. The process of  claim 28  wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 
     
     
       30. The process of  claim 28  wherein the molecular sieve is at least one of zeolite beta, ZSM-12, MCM-68 SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 
     
     
       31. The process of  claim 29  wherein the molecular sieve is ZSM-48. 
     
     
       32. The process of  claim 28  wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400° C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr −1  and a treat gas rate of from 45 to 1780 m 3 /m 3 . 
     
     
       33. The process of  claim 28  wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 
     
     
       34. The process of  claim 33  wherein the improved yield is at least 4 relative percent. 
     
     
       35. The process of  claim 28  wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 
     
     
       36. The process of  claim 28  wherein the dewaxing catalyst bears a metal hydrogenation component. 
     
     
       37. The process of  claim 36  wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 
     
     
       38. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least 15 wt. % wax, based on hydrocarbon, feed which comprises:
 (a) hydrotreating the hydrocarbon feed in the presence of a hydrotreating catalyst under hydrotreating conditions to produce a hydrotreated feed and sulfur- and nitrogen-containing contaminants; 
 (b) separating the hydrotreated feed from the sulfur- and nitrogen-containing contaminants; 
 (c) adding to the separated hydrotreated feed at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether wherein the amount of oxygen in the separated hydrotreated feed mixture is at least about 100 wppm to 10000 wppm measured as oxygen; and 
 (d) contacting the mixture from step (c) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains a molecular sieve containing at least one 10 or 12 ring channel under conditions effective to catalytically dewax the feed. 
 
     
     
       39. The process of  claim 38  wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 
     
     
       40. The process of  claim 38  wherein the molecular sieve is at least one of zeolite bets, ZSM-12, MCM-68 SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 
     
     
       41. The process of  claim 39  wherein the molecular sieve is ZSM-48. 
     
     
       42. The process of  claim 38  wherein the conditions effective to catalytically isomerize the feed include a temperature of from 250 to 400° C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr −1  and a treat gas rate of from 45 to 1780 m 3 /m 3 . 
     
     
       43. The process of  claim 38  wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 
     
     
       44. The process of  claim 43  wherein the improved yield is at least 4 relative percent. 
     
     
       45. The process of  claim 38  wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 
     
     
       46. The process of  claim 38  wherein the dewaxing catalyst bears a metal hydrogenation component. 
     
     
       47. The process of  claim 46  wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 
     
     
       48. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least about 15 wt % wax, based on hydrocarbon feed, which comprises:
 (a) forming a mixture containing the hydrocarbon feed and water wherein the amount of oxygen in the mixture is at least about 100 wppm to 10000 wppm, measured as oxygen, and 
 (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains at least one molecular sieve containing at least one 10 or 12 ring channel under conditions effective to catalytically dewax the feed. 
 
     
     
       49. A process for catalytically dewaxing a mineral hydrocarbon feed containing at least 15 wt. % wax, based on hydrocarbon feed which comprises:
 (a) forming a mixture containing the hydrocarbon feed and at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether wherein the amount of oxygen in the mixture is at least about 100 wppm to 1000 wppm, measured as oxygen, and 
 (b) contacting the mixture from step (a) with a dewaxing catalyst which is ZSM-48 under conditions effective to catalytically dewax the feed. 
 
     
     
       50. The process of  claim 49  wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400° C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr −1  and a treat gas rate of from 45 to 1780 m 3 /m 3 . 
     
     
       51. The process of  claim 49  wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 
     
     
       52. The process of  claim 49  wherein the improved yield is at least 4 relative percent. 
     
     
       53. The process of  claim 52  wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 
     
     
       54. The process of  claim 49  wherein the dewaxing catalyst bears a metal hydrogenation component. 
     
     
       55. The process of  claim 54  wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 
     
     
       56. A process for catalytically dewaxing a Fischer-Tropsch wax containing greater than 0.5 wppm sulfur, based on Fischer-Tropsch wax, which comprises:
 (a) forming a mixture containing the hydrocarbon feed and at least one oxygenate wherein the amount of oxygenate in the mixture is at least about 100 wppm to 10000 wppm, measured as oxygen, and 
 (b) contacting the mixture from step (a) with a dewaxing catalyst which functions by isomerizing waxy molecules and contains at least one molecular sieve containing at least one 10 or 12 ring under conditions effective to catalytically dewax the feed. 
 
     
     
       57. The process of  claim 56  wherein the oxygenate is at least one alcohol, carboxylic acid, ester, aldehyde, ketone or ether. 
     
     
       58. The process of  claim 56  wherein the oxygenate is water. 
     
     
       59. The process of  claim 56  wherein the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, EU-1, NU-87, SAPO-11, SAPO-41, ITQ-13 or MCM-71. 
     
     
       60. The process of  claim 56  wherein the molecular sieve is at least one of zeolite beta, ZSM-12, MCM-68, SAPO-5, SAPO-31, MAPO-36, ZSM-18, offretite, mordenite or faujasite. 
     
     
       61. The process of  claim 59  wherein the molecular sieve is ZSM-48. 
     
     
       62. The process of  claim 56  wherein the conditions effective to catalytically dewax the feed include a temperature of from 250 to 400° C., a pressure of from 791 to 20786 kPa, a liquid hourly space velocity of from 0.1 to 10 hr −1  and a treat gas rate of from 45 to 1780 m 3 /m 3 . 
     
     
       63. The process of  claim 56  wherein catalytic dewaxing of feed results in improved yield of isomerate boiling in the lube oil range at equivalent pour over the dewaxing catalyst without oxygenate treatment. 
     
     
       64. The process of  claim 63  wherein the improved yield is at least 4 relative percent. 
     
     
       65. The process of  claim 56  wherein the dewaxing catalyst is sulfided, reduced, or sulfided and reduced. 
     
     
       66. The process of  claim 56  wherein the dewaxing catalyst bears a metal hydrogenation component. 
     
     
       67. The process of  claim 56  wherein the metal hydrogenation component is at least one Group 9 or 10 noble metal. 
     
     
       68. The process of  claim 56  wherein the Fischer-Tropsch wax is hydrotreated prior to step (a).

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